Trichloromethane sulphenic acid derivatives and their use in the combatting of fungi



United States Patent TRICHLOROMETHANE SULPHENIC ACID DERIV- ATIXF EIJSkrEND IHEIR USE IN THE COMBATTING OF I Hans Gysin and Alfred Margot, Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland No Drawing. Original application October 27, 1953, Se-

rial No. 388,674. Divided and this application March 16, 1956, Serial No. 571,900

. ,2. Claims. (Cl. 260-556) The present invention is concerned with new trichloromethane sulphenic acid derivatives, their production and their use in combatting fungi. U. S. Patent No. 2,553,775 claims trichloromethane sulphenic acid amides, the amide group of which is substituted by an acyl radical. As compounds with a sulphonic acid radical as acyl substituent of the amide group, benzene sulphone-N -trichloromethane sulphenyl anilide and benzene sulphone-N-trichloromethane sulphenyl-N-butyl amide are cited. On the other hand, trichloromethane sulphenamides acylated by methane sulphonic acid have not been known up to the present. It has now been found that such compounds of the general formula:

S--C Ola CHHOJI wherein X represents hydrogen or another monovalent cation such as an alkali metal cation, with trichloromethane sulphenyl chloride (perchloromethyl mercaptan). Good yields are obtained.

The reactions mentioned above can be performed in water or in inert organic solvents. If salts of the suling agents, in water e. g. with caustic soda lye. It can be accelerated in organic solvents also with sodium or potassium carbonate or acetate or also with tertiary organic bases.

N-methane sulphonyl derivatives of 2-, 3- and 4-chloraniline are the sulphonic acid amides of the general formula:

C HaS OPNHO EXAMPLE 1 om-s 014 001 ClsC-S I 20.5 parts of methane sulphone-4-chloranilide are dissolved in 200 parts by volume of 0.5 N-caustic soda lye and, while stirring well at about 10, 18.6 parts of perchloromethyl mercaptan are added. After stirring for some hours at room temperature, caustic soda lye is added to the reaction mixture which by this "time has an acid reaction, until the reaction is phenolphthaleini alkaline. The precipitate is drawn off under suction and washed well with Water. The methane sulphone-N-trichloromethane sulphenyl-4-chloranilide so obtained melts at 1l4-115 after recrystallisation from cyclohexane.

Methane sulphone-N-trichloromethane sulphenyl 2- chloranilide (M. P. l29l30) for example can be produced in the same way.

The excellent fungicidal activity of the new compounds according to this invention can be seen from the results of slide germination tests which are summarised in the following tables.

In the tables, that amount of the tested compounds is given in '7 per square centimetre which was able to prevent the germination in a damp atmosphere of at least W of the pores spread on the slides. The active coatings were obtained by distributing uniformly the acetone solution of the compounds in different concentrations on the slides and allowing the solvent to evaporate; 4 slides were used for each coating tested of each compound.

Table I Compound (T=-SO Ch) Necessary amount in 7 per cm. to prevent germination of the spores of Alter- Alter- Conio- Fusar- M acro- Penicilnaria naria Botrytis thy mam ium culsporiu'm hum Rosae tenuis chinerea diplomorium spec. crustadiella ceum Cl 1 CHz-SOz-NT 13 13 1.3 1s 1s 13 1a 2 CH3SOg-NT 3C1 1.3 1.3 1.3 1.3 1.3 1.3 1.3

phonic acid amides are not used as starting materials, the recation can be accelerated by the addition of acid bind- Contrary to the new methane sulphone-N-trichloromethane sulphenyl anilides, the benzene sulphone-N-tri- 3 chloromethane su1ph'enyl"anilide inhibits the germination of'thespores' ofonlyone of the threefungi which were' tested, as shown in Table II.

In field trials, compound No. 2, methane sulphone-N- tr'ichloromethane sulphenyl-4-chloranilide, gave particularlygood results;

Thenew'sulphenic acid amide derivatives'canbe used for the protection-of plants and parts-thereoffrom attackby injurious fungi, either as such or combinedwith suitable carriers and dispersing agents and-also if desired with other fungicidal or insecticidal substances. They are suitable for the treatmentof organic materials such as, e. g. wood, textiles, hides and leather.

For example, the active ingredients can be combined with solid pulverulent carriers such as, e. g. talc, kaolin, bole, bentonite, chalk, ground limestone, and the pulverulentfungicides so obtained can'be made water suspendible if desired by the addition of wetting and dispersing'agents. Further, the active ingredients -can be dispersed inwater with the aid of suitable emulsifying agents-or dissolved'in organic solvents, e. g. chlorinated hydrocarbons-such as trichlorethylene or in medium petroleum fractions, if desired with the addition of auxiliary solventssuch as acetone or-higher ketones. Another use for the active ingredients is their dispersal in the air in the" form of aerosols; smoke or' steam', in particular; e: g. in store rooms and greenhouses.

EXAMPLE 2 By grinding 10 parts of"active ingredient with 82 parts ofzkaolin or, chalkxand mixing with'8 parts of wetting and dispersing. agents, e. g. 8 parts of sulphite waste liquor, a concentrate is obtained which, on mixingwith water, gives a fungicidal sprayingagent which is excellently suited for'tlie treatment of theparts 'of plants above the ground; Methane sulphone N trichloromethane sulphenyl-4 chloranilide can be'used as active ingredient.

EXAMPLE 4 3 A concentrate. for theproduction of emulsions is obtained by mixing2'5 parts of methane sulphonic acid-N- trichloromethane sulphenyl-4-chloranilide, 67 parts of Xylene and8 parts of a polyethylene oxide esterified with ricinoleic acid;

1 part of this concentrate is dispersed in 200 to parts offwater to give agents ready for use containing 0.05 to-0.5%- of active'ingredient.

1. Tiichlorometlianesulphenicacid derivatives correspendingto. the general formula:

GMT-S Cl 2. The compound of the formula;

cho -s.

I CHarSOz-N-O-Ol 2,553,770. Kittleson May, 22, 1951 

1. TRICHLOROMETHANE SULPHENIC ACID DERIVATIVES CORRESPONDING TO THE GENERAL FORMULA: 